JPH03212401A - Preparation of polybutadiene having particle size increased by emulsion polymerization - Google Patents
Preparation of polybutadiene having particle size increased by emulsion polymerizationInfo
- Publication number
- JPH03212401A JPH03212401A JP2330945A JP33094590A JPH03212401A JP H03212401 A JPH03212401 A JP H03212401A JP 2330945 A JP2330945 A JP 2330945A JP 33094590 A JP33094590 A JP 33094590A JP H03212401 A JPH03212401 A JP H03212401A
- Authority
- JP
- Japan
- Prior art keywords
- latex
- emulsion polymerization
- particle size
- polymerization medium
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/065—Increasing the size of dispersed rubber particles
- C08C1/07—Increasing the size of dispersed rubber particles characterised by the agglomerating agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
発明の分野
本発明は、増大した平均粒度を有するポリブタジェンの
製造方法に関する。更に詳しくは、本発明は増大した平
均粒度を有するポリブタジェンを製造するための乳化重
合方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing polybutadiene with increased average particle size. More particularly, the present invention relates to an emulsion polymerization process for producing polybutadiene with increased average particle size.
発明の背景
一定の温度及び固形分でのポリブタジェンを含む合成ゴ
ムラテックスの粘度は、ポリブタジェンの平均粒度及び
粒度分布に大きく影響される。BACKGROUND OF THE INVENTION The viscosity of synthetic rubber latexes containing polybutadiene at a given temperature and solids content is strongly influenced by the average particle size and particle size distribution of the polybutadiene.
般的に、高い平均粒度が望ましく、その結果一定の固形
分及び温度において低い粘度のラテックスを与える。乳
化重合の間にゴムラテックスの粒度を高めるために、様
々な方法が用いられてきた。Generally, a high average particle size is desirable, resulting in a latex with low viscosity at a given solids content and temperature. Various methods have been used to increase the particle size of rubber latex during emulsion polymerization.
しかし、これらの方法の夫々が困難を生じた。However, each of these methods presented difficulties.
例えば、チッテンデンら（ＣｈｉＮｅｎｄｅｎ ｅｊ
ａｌ） 。For example, Chittenden et al.
al).
（１９４８）及びポーダースら（Ｂｏｒｄｅｒｓ ａｔ
ａｌ）
３ （１９４８）に、ブタジェンの乳化重合反応の間に
凝集を促進するために、高い有機単量体対水の比及び低
いセッケン濃度を用いることが開示されている。しかし
、この方法は１回又は数回の不安定期をもたらし、その
間に凝固が起きる可能性がある。また、高粘度条件であ
るために熱除去が困難となる可能性があり、そして臨界
的な粒子の合体段階の間に反応が制御されない状態で進
行した場合、望ましい反応結果を再現することがしばし
ば困難となる。(1948) and Borders at
al) 3 (1948) discloses the use of high organic monomer to water ratios and low soap concentrations to promote flocculation during the emulsion polymerization reaction of butadiene. However, this method results in one or several periods of instability during which clotting may occur. Additionally, heat removal can be difficult due to high viscosity conditions, and it is often difficult to reproduce the desired reaction outcome if the reaction proceeds uncontrolled during the critical particle coalescence step. It becomes difficult.
また、粒度を高めるためにゴムラテックスにコロイド活
性化合物を加えることも知られている。It is also known to add colloidal active compounds to rubber latex to increase particle size.
例えば、ハウランドらの米国特許第３． ０５６゜７５
８号明細書に、粒度を高めるために合成ゴムラテックス
にポリビニルメチルエーテルを加えることが教示されて
おり、またシュルターの米国特許第３．３３０，７９５
号明細書に、凝集を起こすために合成ゴム分散液にポリ
アルキレンオキシドを加えることが開示されている。そ
のほか、乳化重合処方にコロイド活性化合物を加えるこ
とも試みられている。例えば、ベルギー特許第８１７゜
５０５号明細書に乳化反応へのポリアルキレングリコー
ル凝集剤の添加が開示されており、またア１、Ｖｏｌ、
１９．Ｎｏ、 ７． ８６３ （１９８７）に
乳化反応へのアルギン酸ナトリウムと硫酸マグネシウム
の添加が開示されている。しかし、これらの方法はしば
しば低い単量体転化速度をもたらし、反応が完了までに
７０時間の長時間を要する可能性がある点に不都合があ
る。For example, Howland et al., US Patent No. 3. 056°75
No. 8 teaches the addition of polyvinyl methyl ether to synthetic rubber latex to increase particle size, and Schurter, U.S. Pat.
No. 5,923,603 discloses the addition of polyalkylene oxide to a synthetic rubber dispersion to cause agglomeration. Additionally, attempts have been made to add colloidally active compounds to emulsion polymerization formulations. For example, Belgian Patent No. 817.505 discloses the addition of a polyalkylene glycol flocculant to an emulsification reaction, and A1, Vol.
19. No, 7. 863 (1987) discloses the addition of sodium alginate and magnesium sulfate to the emulsification reaction. However, these methods often result in low monomer conversion rates and have the disadvantage that the reaction can take as long as 70 hours to complete.
ガラスラーの米国特許第３．３１８，８３１号明細書に
、重合の間に高ぜん新法を用いて短い反応時間で大粒径
ラテックスを製造する方法が開示されている。しかし、
この方法は高いかくはん速度が可能な特殊な反応器を必
要とする点に不都合がある。Glaslar, US Pat. No. 3,318,831, discloses a method for producing large particle size latex in short reaction times using a high-density process during polymerization. but,
This method has the disadvantage that it requires a special reactor capable of high agitation rates.
従って、高粒度の合成ゴムラテックスを得る改良された
方法の必要性が依然としである。Therefore, there remains a need for improved methods of obtaining high particle size synthetic rubber latexes.
発明の概要
従って、本発明の目的は高粒度の合成ゴムラテックスを
製造する改良された方法を提供することにある。本発明
のもう１つの目的は、高粒度のポリブタジェンの製造方
法を提供することにある。SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an improved method for producing high particle size synthetic rubber latex. Another object of the present invention is to provide a method for producing high particle size polybutadiene.
本発明の更にもう１つの目的は、高粒度のポリブタジエ
ンを製造するための乳化重合方法を提供することにある
。Yet another object of the present invention is to provide an emulsion polymerization process for producing high particle size polybutadiene.
これらの、そしてその他の目的は、ブタジェンの乳化重
合方法に関する本発明により達成される。These and other objects are achieved by the present invention, which relates to a process for emulsion polymerization of butadiene.
本発明により、重合反応の間に、得られるポリブタジェ
ンラテックスの平均粒度を高めるのに有効な量のアクリ
ルラテックスを乳化重合媒質に加える。本発明方法は、
一般に温度及びか（はん速度に敏感でない点、乳化重合
反応の間にバルク不安定期を誘起しない点、及びアクリ
ルラテックスが導入されると反応が迅速に進行する点で
有利である。また、得られるポリブタジェンラテックス
の粒子も望ましい球形を示す。According to the present invention, an amount of acrylic latex is added to the emulsion polymerization medium during the polymerization reaction in an amount effective to increase the average particle size of the resulting polybutadiene latex. The method of the present invention includes
It is generally advantageous in that it is not sensitive to temperature and heating rate, it does not induce a bulk instability period during the emulsion polymerization reaction, and the reaction proceeds rapidly when acrylic latex is introduced. The polybutadiene latex particles also exhibit the desired spherical shape.
これらの、そして他の目的及び利点は、以下の詳細な説
明により更に十分に理解される。These and other objects and advantages will be more fully understood from the detailed description below.
詳細な説明
本発明は、重合反応の間に、得られるポリブタジェンラ
テックスの平均粒度を高めるのに有効な量のアクリルラ
テックスを乳化重合媒質に加えるブタジェンの乳化重合
方法に関する。DETAILED DESCRIPTION The present invention relates to a process for the emulsion polymerization of butadiene in which an amount of acrylic latex is added to the emulsion polymerization medium during the polymerization reaction in an amount effective to increase the average particle size of the resulting polybutadiene latex.
本発明の合成ゴムラテックスの製造において、例えばブ
タジェン−１，３，２−メチルブタジェン−１，３（イ
ソプレン）、２．３−ジメチルブタジェン−１，３及び
ピペリレンを包含するブタジェン−１，３の１種又はそ
れ以上を使用することができる。また、１種又はそれ以
上の前記ブタジェン−１，３と、該ブタジェン−１，３
とゴム状共重合体を形成する能力を有する１種又はそれ
以上のコモノマーとの混合物を使用することもできる。In the production of the synthetic rubber latex of the present invention, for example, butadiene-1, including butadiene-1,3,2-methylbutadiene-1,3 (isoprene), 2,3-dimethylbutadiene-1,3, and piperylene, One or more of 3 can be used. Also, one or more of the above butadiene-1,3 and the butadiene-1,3
It is also possible to use mixtures of comonomers with one or more comonomers capable of forming rubbery copolymers.
好適なコモノマーには、少なくとも１個の遊離の原子価
が電気陰性基、即ち分子の電気的非対称性又は極性を実
質的に高める基と結合している、ＣＨ２＝Ｃ＜基を含む
１種又はそれ以上のモノエチレン性化合物が包含される
。ブタジェンと共重合可能な前記化合物の例は、スチレ
ン、ビニルトルエン、α−メチルスチレン、クロロスチ
レン、ジクロロスチレン及びビニルナフタレン等のアリ
ールオレフィンであり、スチレンが好適なコモノマーで
ある。前記コモノマーは、得られる単量体混合物の約５
０重量％までの量でブタジェンと共に含まれ得る。Suitable comonomers include one or More monoethylenic compounds are included. Examples of said compounds copolymerizable with butadiene are aryl olefins such as styrene, vinyltoluene, alpha-methylstyrene, chlorostyrene, dichlorostyrene and vinylnaphthalene, with styrene being the preferred comonomer. The comonomer accounts for about 5% of the resulting monomer mixture.
It may be included with butadiene in amounts up to 0% by weight.
前述した様に、前記アクリルラテックスを、重合反応の
間にブタジェン及び必要に応じてコモノマーを含む乳化
重合媒質に、得られるポリブタジェンラテックスの平均
粒度を高めるのに有効な量で加える。好ましくは、前記
アクリルラテックスを、得られるポリブタジェンラテッ
クスの平均粒度を濁り度法により測定して少なくとも約
２００ナノメートルに高めるのに有効な量で乳化重合媒
質に加える。通常、前記アクリルラテックスを、乾燥量
基準で乳化重合媒質中に含まれるブタジェン１００重量
部あたり少なくとも約０．１重量部の量で乳化重合媒質
に加える。好ましくは、前記アクリルラテックスを、乾
燥量基準で乳化重合媒質中に含まれるブタジェン１００
重量部あたり約０．１乃至約１０重量部の量で、更に好
ましくは約１乃至約５重量部の量で加える。As previously mentioned, the acrylic latex is added to the emulsion polymerization medium containing butadiene and optional comonomer during the polymerization reaction in an amount effective to increase the average particle size of the resulting polybutadiene latex. Preferably, the acrylic latex is added to the emulsion polymerization medium in an amount effective to increase the average particle size of the resulting polybutadiene latex to at least about 200 nanometers as measured by turbidimetry. Typically, the acrylic latex is added to the emulsion polymerization medium in an amount of at least about 0.1 parts by weight per 100 parts by weight of butadiene contained in the emulsion polymerization medium on a dry basis. Preferably, the acrylic latex contains 100% butadiene, on a dry basis, contained in the emulsion polymerization medium.
It is added in an amount of about 0.1 to about 10 parts by weight, more preferably about 1 to about 5 parts by weight.
一般的に、本発明方法において使用するのに好適な前記
アクリルラテックスは、当業界で周知のアクリルラテッ
クスの何れから成っていても良い。Generally, the acrylic latex suitable for use in the method of the invention may consist of any of the acrylic latexes well known in the art.
好適な態様においては、前記アクリルラテックスはポリ
（アクリル酸アルキル）ラテックス又はポリ（メタクリ
ル酸アルキル）ラテックスから成る。In a preferred embodiment, the acrylic latex comprises poly(alkyl acrylate) latex or poly(alkyl methacrylate) latex.
下記実施例において示した様に、本発明方法において使
用する特に好適なアクリルラテックスはポリ（アクリル
酸プチルーコーメタクリル酸）ラテックス等のポリ（ア
クリル酸アルキル−コーメタクリル酸）ラテックスから
成る。As shown in the Examples below, a particularly preferred acrylic latex for use in the process of the invention comprises a poly(alkyl acrylate-co-methacrylic acid) latex, such as a poly(butyl-co-methacrylic acid) latex.
ブタジェンの乳化重合の一般的な方法は、当業界で周知
である。典型的には、前記乳化重合媒質にはセッケン又
は界面活性剤、遊離基開始剤及び連鎖移動剤が含まれ、
それらの全てが当業界で周知である。適切なセッケン／
界面活性剤の例には、脂肪酸セッケン、そして特に例え
ばラウリン酸、ミリスチン酸、パルミチン酸、オレイン
酸及びステアリン酸のナトリウム又はカリウム塩等の水
溶性長鎖脂肪酸セッケンが包含される。トール油の水溶
性ナトリウム又はカリウムセッケン、及び不均化ロジン
セッケンを包含するロジンセッケンを使用することもで
きる。所望する場合、第２の界面活性剤が存在してもよ
く、その例には、アルキルナフタレンスルホン酸ナトリ
ウム等の、アリールスルホン酸から誘導されるスルホン
酸アルカリ金属塩が包含される。適切な遊離基開始剤に
は、有機ヒドロペルオキシド及びイオン化可能な重金属
塩が包含される。適切な連鎖移動剤には、周知のメルカ
プタン型化合物が包含される。General methods for emulsion polymerization of butadiene are well known in the art. Typically, the emulsion polymerization medium includes a soap or surfactant, a free radical initiator and a chain transfer agent;
All of them are well known in the art. Appropriate soap/
Examples of surfactants include fatty acid soaps and especially water-soluble long chain fatty acid soaps such as the sodium or potassium salts of lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid. Rosin soaps can also be used, including tall oil water-soluble sodium or potassium soaps, and disproportionated rosin soaps. If desired, a second surfactant may be present, examples of which include alkali metal sulfonates derived from aryl sulfonic acids, such as sodium alkylnaphthalene sulfonates. Suitable free radical initiators include organic hydroperoxides and ionizable heavy metal salts. Suitable chain transfer agents include the well-known mercaptan type compounds.
当業者は、乳化重合反応の最初または途中でのアクリル
ラテックスの添加により、先行技術で用いられたコロイ
ド活性剤の添加で経験するのと同様の結果が得られる、
即ち粒子が形成直後に凝集し始め、これにより反応の初
期に粒子数が減少し、極めて長い反応時間をもたらすも
のと考える。しかし本発明者は、実際は本発明方法によ
り長い反応時間を必要とせずに高粒度の合成ゴムラテッ
クス粒子が形成され得ることを見い出した。本発明を以
下の記載により減縮する意図はないが、本発明者は、過
半量の単量体が高粒子数運動論の利点を有する小粒子に
重合し、そしてその後粒子が凝集した後に反応が完了し
、これにより減少した反応時間で大きい粒度の粒子が得
られるものと確信する。また、単量体膨潤粒子が一層柔
かく、そして凝集の間に一層変形し易く、これにより完
全な粒子の合体が得られると考えられる。重合完了の間
の球形粒子の形成への自然な傾向と組合わさった粒子の
合体により、望ましい球形の粒子が得られる。Those skilled in the art will appreciate that the addition of acrylic latex at the beginning or during the emulsion polymerization reaction produces results similar to those experienced with the addition of colloidal activators used in the prior art.
That is, it is believed that the particles begin to aggregate immediately after formation, which reduces the number of particles at the beginning of the reaction, resulting in an extremely long reaction time. However, the inventors have found that high particle size synthetic rubber latex particles can actually be formed by the method of the present invention without requiring long reaction times. While not intending to limit the invention by the following description, the inventors have discovered that the majority of the monomers polymerize into small particles that have the advantage of high particle number kinetics, and that the reaction occurs after the particles have aggregated. We believe that this results in large particle size particles with reduced reaction time. It is also believed that the monomer swollen particles are softer and more deformable during aggregation, resulting in complete particle coalescence. Particle coalescence combined with the natural tendency to form spherical particles during polymerization completion results in the desired spherical particles.
本発明方法は、アクリルラテックスで誘起される凝集が
一般に温度及びかくはん速度に敏感ではない点、この方
法が乳化重合プロセスにバルク不安定期を誘発させない
点、及びアクリルラテックスを導入すると重合反応が極
めて迅速に生起する点で有利である。また、アクリルラ
テックス添加後にもたらされる小さい粒子も凝集すると
考えられる。アクリルラテックスに′よるこれら新たな
粒子の凝集は、他の重合／凝集方法により製造されるも
のよりも狭い粒度分布をもたらす。粒子が凝集したとき
の総表面積の減少により、反応条件が防止しない限り通
常は新たな小粒子の生成をもたらすセッケンの脱離が生
起する。The method of the present invention is characterized by the fact that acrylic latex-induced agglomeration is generally not sensitive to temperature and agitation rate, that the method does not induce bulk instability periods in the emulsion polymerization process, and that the polymerization reaction is extremely rapid when the acrylic latex is introduced. It is advantageous in that it occurs in It is also believed that the small particles that result after addition of the acrylic latex also aggregate. The agglomeration of these new particles by the acrylic latex results in a narrower particle size distribution than those produced by other polymerization/aggregation methods. The reduction in total surface area when particles agglomerate results in desorption of the soap, which usually results in the formation of new small particles unless reaction conditions prevent it.
以下の実施例により、本発明の特定の態様を例証する。The following examples illustrate certain embodiments of the invention.
実施例１
１２オンスのクエン酸塩ボトルに、１００重量部のブタ
ジェン、３．５重量部のオレイン酸カリウム、０．３５
６重量部のピロリン酸四ナトリウム、０．１４重量部の
ペルオキシ硫酸カリウム、０．２重量部のｔｅｒｔ−ド
デシルメルカプタン及び２３０重量部の脱塩水を装入し
、その後ゴム隔膜を取付けた。重合を開始させるために
、この媒質を４９℃で７時間加熱した。その後温度を６
５℃に高め、そして２．０重量部（乾燥量基準）のアク
リルラテックス凝集剤を加えた。前記アクリルラテック
スは、２０／８０のメタクリル酸／アクリル酸ブチル共
重合体から成っていた。得られたポリブタジェンラテッ
クスは、濁り度法で測定して３３０ｎｍの粒度を有して
いた。Example 1 In a 12 oz citrate bottle, 100 parts by weight butadiene, 3.5 parts by weight potassium oleate, 0.35 parts by weight.
6 parts by weight of tetrasodium pyrophosphate, 0.14 parts by weight of potassium peroxysulfate, 0.2 parts by weight of tert-dodecylmercaptan and 230 parts by weight of demineralized water were charged, and then a rubber diaphragm was attached. The medium was heated at 49° C. for 7 hours to initiate polymerization. Then increase the temperature to 6
The temperature was raised to 5° C. and 2.0 parts by weight (dry basis) of acrylic latex flocculant was added. The acrylic latex consisted of a 20/80 methacrylic acid/butyl acrylate copolymer. The resulting polybutadiene latex had a particle size of 330 nm as measured by turbidity.
実施例２
圧力反応器に、１００重量部のブタジェン、３゜５重量
部のオレイン酸カリウム、０．３５６重量部のピロリン
酸四ナトリウム、０．２重量部のｔｅｒｔ−ドデシルメ
ルカプタン及び２２０重量部の脱塩水を装入した。混合
物をかくはんしながら１４０″Ｆに加熱した。その後、
１０．０重量部の脱塩水に溶解した０、１４重量部のペ
ルオキシ硫酸カリウムをショット法により加えて重合を
開始させた。ポリマーへの転化率６５％で、温度を１５
５″Ｆに高めた。ポリマーへの転化率８０％で、急速混
合を促進するためにかくはんを強め、そして３．０重量
部（乾燥量基準）の実施例１に記載したアクリルラテッ
クス凝集剤をショット法により加えた。１分後、かくは
ん速度を通常に戻した。Example 2 A pressure reactor was charged with 100 parts by weight of butadiene, 3.5 parts by weight of potassium oleate, 0.356 parts by weight of tetrasodium pyrophosphate, 0.2 parts by weight of tert-dodecyl mercaptan, and 220 parts by weight of Charged with demineralized water. The mixture was heated to 140″F with stirring. Then,
Polymerization was initiated by adding 0.14 parts by weight of potassium peroxysulfate dissolved in 10.0 parts by weight of demineralized water by the shot method. At 65% conversion to polymer, the temperature was increased to 15%.
At 80% conversion to polymer, agitation was increased to promote rapid mixing, and 3.0 parts by weight (dry basis) of the acrylic latex flocculant described in Example 1 was added. It was added by shot method. After 1 minute, the stirring speed was returned to normal.
反応を継続し、そして１７時間で９１．５％の転化率ま
で行ない、０．２％未満の凝固塊を含み、濁り度法で測
定して２９０ナノメートルの平均粒径及び下記粒度分布
：２．８５重量％〈径１００ナノメートル、３４．５重
量％〈径２５０ナノメートル、及び９９．０２重量％〈
径４００ナノメートル、を有するラテックスを得た。得
られたポリブタジェンは、スチレン及びアクリロニトリ
ルでグラフトするのに十分に安定であり、そして様々な
熱可塑性樹脂における衝撃変性剤として有用であった。The reaction was continued and carried out to a conversion of 91.5% in 17 hours, containing less than 0.2% coagulum, with an average particle size of 290 nanometers as measured by turbidity and a particle size distribution of: 2 .85 wt%〈100 nm diameter, 34.5 wt%〈250 nm diameter, and 99.02 wt%〈
A latex having a diameter of 400 nanometers was obtained. The resulting polybutadiene was stable enough to be grafted with styrene and acrylonitrile and was useful as an impact modifier in various thermoplastics.
実施例３
本実施例においては、実施例２で用いた３、０重量部（
乾燥量基準）のアクリルラテックス凝集剤に代えて、５
．０重量部（乾燥量基準）の前記アクリルラテックス凝
集剤を用いた以外は、実施例２で用いたのと同様の方法
でポリブタジェンを製造した。反応を１７時間で９１．
０％の転化率まで行ない、そして濁り度法で測定して２
４５ナノメートルの平均粒径を有し、そして０．０１％
未満の凝固塊を含むラテックスを得た。このラテックス
も、スチレン及びアクリロニトリルを用いたグラフト化
に対して安定であった。Example 3 In this example, 3.0 parts by weight (
In place of the acrylic latex flocculant (on a dry basis),
．． Polybutadiene was produced in the same manner as in Example 2, except that 0 parts by weight (dry basis) of the acrylic latex flocculant was used. The reaction was carried out for 17 hours at a temperature of 91.
0% conversion and measured by turbidity method.
has an average particle size of 45 nanometers and 0.01%
A latex containing less than 10% coagulum was obtained. This latex was also stable to grafting with styrene and acrylonitrile.
以上の実施例は、本発明の特定の態様を例証するために
示したものであり、本発明の方法及び製品の範囲を減縮
することを意図したものではない。The foregoing examples are presented to illustrate certain aspects of the invention and are not intended to limit the scope of the methods and products of the invention.
請求の範囲に記載した本発明の範囲内の他の態様及び利
点は、当業者にとって明らかである。Other aspects and advantages within the scope of the claimed invention will be apparent to those skilled in the art.
Claims (14)
乳化重合する方法において、重合反応の間に前記乳化重
合媒質に、得られるポリブタジエンラテックスの平均粒
度を高めるのに有効な量のアクリルラテックスを加える
ことにより改良した方法。(1) In a method of emulsion polymerizing butadiene in an emulsion polymerization medium containing butadiene, an amount of acrylic latex effective to increase the average particle size of the resulting polybutadiene latex is added to the emulsion polymerization medium during the polymerization reaction. A method improved by.
ラテックスの平均粒度を濁り度法により測定して少なく
とも約２００ナノメートルに高めるのに有効な量で乳化
重合媒質に加える請求項１記載の方法。2. The method of claim 1, wherein the acrylic latex is added to the emulsion polymerization medium in an amount effective to increase the average particle size of the resulting polybutadiene latex to at least about 200 nanometers as measured by turbidity.
質中に含まれるブタジエン１００重量部あたり少なくと
も約０．１重量部の量で乳化重合媒質に加える請求項１
記載の方法。(3) The acrylic latex is added to the emulsion polymerization medium in an amount of at least about 0.1 parts by weight per 100 parts by weight of butadiene contained in the emulsion polymerization medium on a dry basis.
Method described.
質中に含まれるブタジエン１００重量部あたり約０．１
乃至約１０重量部の量で乳化重合媒質に加える請求項１
記載の方法。(4) About 0.1 part by weight of acrylic latex per 100 parts by weight of butadiene contained in the emulsion polymerization medium on a dry basis.
Claim 1 added to the emulsion polymerization medium in an amount of from about 10 parts by weight.
Method described.
質中に含まれるブタジエン１００重量部あたり約１乃至
約５重量部の量で乳化重合媒質に加える請求項１記載の
方法。5. The method of claim 1, wherein the acrylic latex is added to the emulsion polymerization medium in an amount of from about 1 to about 5 parts by weight per 100 parts by weight of butadiene contained in the emulsion polymerization medium on a dry basis.
）ラテックスから成る請求項１記載の方法。(6) The method of claim 1, wherein the acrylic latex comprises poly(alkyl acrylate) latex.
ル）ラテックスから成る請求項１記載の方法。(7) The method of claim 1, wherein the acrylic latex comprises poly(alkyl methacrylate) latex.
−コーメタクリル酸）ラテックスから成る請求項１記載
の方法。(8) The method of claim 1, wherein the acrylic latex comprises poly(alkyl acrylate-comethacrylic acid) latex.
コーメタクリル酸）ラテックスから成る請求項８記載の
方法。(9) Acrylic latex is poly(butyl acrylate)
9. The method of claim 8, comprising co-methacrylic acid) latex.
始剤及び連鎖移動剤を含む請求項１記載の方法。10. The method of claim 1, wherein the emulsion polymerization medium further comprises a soap, a free radical initiator, and a chain transfer agent.
るコモノマーを含む請求項１記載の方法。11. The method of claim 1, wherein the emulsion polymerization medium additionally contains a comonomer that polymerizes with butadiene.
の方法。(12) The method of claim 11, wherein the comonomer comprises styrene.
ックスの平均粒度を高めるのに有効な量のアクリルラテ
ックスを乳化重合媒質に加える工程を含む乳化重合方法
により製造されるポリブタジエンラテックス。(13) A polybutadiene latex made by an emulsion polymerization process comprising adding to the emulsion polymerization medium an amount of acrylic latex effective to increase the average particle size of the resulting polybutadiene latex during the polymerization reaction.
ある請求項１３記載のポリブタジエンラテックス。14. The polybutadiene latex of claim 13, wherein the average particle size is at least about 200 nanometers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US454,544 | 1989-12-21 | ||
| US07/454,544 US5294659A (en) | 1989-12-21 | 1989-12-21 | Method for preparing emulsion polymerized polybutadiene of increased particle size |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03212401A true JPH03212401A (en) | 1991-09-18 |
| JP3162703B2 JP3162703B2 (en) | 2001-05-08 |
Family
ID=23805043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33094590A Expired - Fee Related JP3162703B2 (en) | 1989-12-21 | 1990-11-30 | Process for producing polybutadiene with increased particle size by emulsion polymerization |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5294659A (en) |
| EP (1) | EP0433710B1 (en) |
| JP (1) | JP3162703B2 (en) |
| KR (1) | KR100201674B1 (en) |
| AU (1) | AU647060B2 (en) |
| CA (1) | CA2030615A1 (en) |
| DE (1) | DE69021179T2 (en) |
| ES (1) | ES2075870T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009025334A1 (en) | 2007-08-21 | 2009-02-26 | Umg Abs, Ltd. | Method for producing enlarged rubber, graft copolymer, thermoplastic resin composition and molded article |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336720A (en) * | 1991-06-05 | 1994-08-09 | Rohm And Haas Company | Impact resistant polymers |
| DE4344992A1 (en) * | 1993-12-30 | 1995-07-06 | Huels Chemische Werke Ag | Aqueous, highly concentrated synthetic rubber dispersion and its production |
| US5534594A (en) * | 1994-12-05 | 1996-07-09 | Rohm And Haas Company | Preparation of butadiene-based impact modifiers |
| US5985993A (en) * | 1996-08-01 | 1999-11-16 | Cheil Industries, Inc. | Method for preparing polybutadiene latex |
| KR100380014B1 (en) * | 1998-03-20 | 2003-08-19 | 주식회사 엘지화학 | Method for preparing rubbery polymer latex |
| US6184287B1 (en) * | 1999-01-26 | 2001-02-06 | Omnova Solutions Inc. | Polymeric latexes prepared in the presence of 2-acrylamido-2-methylpropanesulfonate |
| KR100576312B1 (en) * | 1999-10-29 | 2006-05-03 | 제일모직주식회사 | Manufacturing method of synthetic rubber latex having large particle diameter |
| US6777483B2 (en) * | 2000-10-27 | 2004-08-17 | Cheil Industries Inc. | Method of preparing diene latex having a large particle size by addition of a pretreated seed latex to an agglomerating agent |
| US20030111770A1 (en) * | 2001-12-13 | 2003-06-19 | Bridgestone Corp. | Method of improving carbon black dispersion in rubber compositions |
| CN1313506C (en) * | 2004-08-04 | 2007-05-02 | 中国石油天然气集团公司 | Polymerization method of after-agglomeration polybutadiene latex, vinyl benzene and acrylonitrile |
| DE102005022632B4 (en) | 2005-05-11 | 2022-05-25 | Ineos Styrolution Europe Gmbh | Particulate rubber, process for its production and use, and graft copolymer, thermoplastic molding material and process for its production |
| CN103059222B (en) * | 2013-01-06 | 2017-02-15 | 杭州蓝诚新材料有限公司 | Preparation method of large-particle-size styrene-butadiene latex |
| CN121609822A (en) * | 2024-08-27 | 2026-03-06 | 中国石油天然气股份有限公司 | Polybutadiene rubber latex, its preparation method and application |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US330795A (en) * | 1885-11-17 | James macphail | ||
| NL252940A (en) * | 1959-06-24 | |||
| FR1337809A (en) * | 1961-09-26 | 1963-09-20 | Us Rubber Co | Synthetic rubber latex of the butadiene polymer type |
| DE1213984B (en) * | 1963-12-05 | 1966-04-07 | Huels Chemische Werke Ag | Process for agglomerating synthetic rubber dispersions |
| US3318831A (en) * | 1963-12-16 | 1967-05-09 | Copolymer Rubber & Chem Corp | Process for preparing high solids concentrated latex |
| JPS5645921B2 (en) * | 1973-07-06 | 1981-10-29 | ||
| US4385164A (en) * | 1976-03-10 | 1983-05-24 | The Goodyear Tire & Rubber Company | Block copolymer dispersion stabilizer and aqueous dispersion polymerization therewith |
| US4308912A (en) * | 1979-03-28 | 1982-01-05 | Knecht Bernath L | Heat transfer system |
| NO860171L (en) * | 1985-01-30 | 1986-07-31 | Japan Synthetic Rubber Co Ltd | PROCEDURE FOR MANUFACTURE OF LARGE POLYMER PARTICLES. |
| JP2508083B2 (en) * | 1987-05-19 | 1996-06-19 | 大日本インキ化学工業株式会社 | Method for producing emulsion polymer |
-
1989
- 1989-12-21 US US07/454,544 patent/US5294659A/en not_active Expired - Fee Related
-
1990
- 1990-11-22 CA CA002030615A patent/CA2030615A1/en not_active Abandoned
- 1990-11-27 EP EP90122618A patent/EP0433710B1/en not_active Expired - Lifetime
- 1990-11-27 DE DE69021179T patent/DE69021179T2/en not_active Expired - Fee Related
- 1990-11-27 ES ES90122618T patent/ES2075870T3/en not_active Expired - Lifetime
- 1990-11-30 JP JP33094590A patent/JP3162703B2/en not_active Expired - Fee Related
- 1990-12-19 AU AU68246/90A patent/AU647060B2/en not_active Ceased
- 1990-12-20 KR KR1019900021153A patent/KR100201674B1/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009025334A1 (en) | 2007-08-21 | 2009-02-26 | Umg Abs, Ltd. | Method for producing enlarged rubber, graft copolymer, thermoplastic resin composition and molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69021179D1 (en) | 1995-08-31 |
| AU647060B2 (en) | 1994-03-17 |
| EP0433710B1 (en) | 1995-07-26 |
| JP3162703B2 (en) | 2001-05-08 |
| KR910011924A (en) | 1991-08-07 |
| CA2030615A1 (en) | 1991-06-22 |
| US5294659A (en) | 1994-03-15 |
| DE69021179T2 (en) | 1996-03-14 |
| EP0433710A3 (en) | 1991-12-04 |
| KR100201674B1 (en) | 1999-06-15 |
| AU6824690A (en) | 1991-06-27 |
| ES2075870T3 (en) | 1995-10-16 |
| EP0433710A2 (en) | 1991-06-26 |
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